Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Chiral imprinting of palladium with cinchona alkaloids

Nature Chemistry volume 1, pages 160–164 (2009)Cite this article

Abstract

In the search for new materials and concepts in materials science, metallo-organic hybrids are attractive candidates; they can combine the rich diversity of organic molecules with the advantages of metals. Transition metals such as palladium are widely applied in catalysis, and small organic molecules such as those in the cinchona alkaloid family can control the stereochemistry of a number of organic reactions. Here, we show that reducing a metal salt in the presence of a cinchona alkaloid dopant gives a chirally imprinted metallo-organic hybrid material that is catalytically active and shows moderate enantioselectivity in hydrogenation. Furthermore, using photoelectron emission spectroscopy, we show that the metal retains some chiral character even after extraction of the dopant. This simple and effective methodology opens exciting opportunities for developing a variety of chiral composite materials.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Hybrid metallo-organic materials prepared from palladium and cinchona alkaloids.
Figure 2: Structural characterization of metallo-organic hybrid materials.
Figure 3: Photoelectron emission spectroscopy of the chirally imprinted palladium.
Figure 4: Stereoselectivity experiments with metallo-organic hybrid materials.

Similar content being viewed by others

References

  1. Callister W. D. Jr in Materials Science and Engineering: An Introduction 5th edn (Wiley, 2000).

    Google Scholar 

  2. Ball, P. in Made to Measure: New Materials for the 21st Century 4th edn (Princeton Univ. Press, 1999).

    Google Scholar 

  3. Behar-Levy, H. & Avnir, D. Entrapment of organic molecules within metals: Dyes in silver. Chem. Mater. 14, 1736–1741 (2002).

    CAS  Google Scholar 

  4. Nesher, G., Gad Marom, G. & Avnir, D. Metal-polymer composites: Synthesis and characterization of polyaniline and other polymer@silver compositions. Chem. Mater. 20, 4425–4432 (2008).

    CAS  Google Scholar 

  5. Yosef, I. & Avnir, D. Metal–organic composites: The heterogeneous organic doping of the coin metals—Copper, silver, and gold. Chem. Mater. 18, 5890–5896 (2006).

    CAS  Google Scholar 

  6. Behar-Levy, H. & Avnir, D. Silver doped with acidic/basic polymers: Novel, reactive metallic composites. Adv. Func. Mater. 15, 1141–1146 (2005).

    CAS  Google Scholar 

  7. Shter, G. E. et al. Organically doped metals—A new approach to metal catalysis: Enhanced Ag-catalyzed oxidation of methanol. Adv. Func. Mater. 17, 913–918 (2007).

    CAS  Google Scholar 

  8. Yosef, I., Abu-Reziq, R. & Avnir, D. Entrapment of an organometallic complex within a metal: A concept for heterogenous catalysis. J. Am. Chem. Soc. 130, 11880–11882 (2008).

    CAS  PubMed  Google Scholar 

  9. Behar-Levy, H., Shter, G. E., Grader, G. S. & Avnir, D. Entrapment of organic molecules within metals 2. Polymers in silver. Chem. Mater. 16, 3197–3202 (2004).

    CAS  Google Scholar 

  10. Behar-Levy, H., Neumann, O., Naaman, R. & Avnir, D. Chirality induction in bulk gold and silver. Adv. Mater. 19, 1207–1211 (2007).

    CAS  Google Scholar 

  11. Goldsmith, M. R. et al. The chiroptical signature of achiral metal clusters induced by dissymmetric adsorbates. Phys. Chem. Chem. Phys. 8, 63–67 (2006).

    CAS  PubMed  Google Scholar 

  12. Kacprzak, K. & Gawronski, J. Cinchona alkaloids and their derivatives: Versatile catalysts and ligands in asymmetric synthesis. Synthesis 961–998 (2001).

  13. Heitbaum, M., Glorius, F. & Escher, I. Asymmetric heterogeneous catalysis. Angew. Chem. Int. Ed. 45, 4732–4762 (2006).

    CAS  Google Scholar 

  14. Ray, K., Ananthavel, S. P., Waldeck, D. H. & Naaman, R. Asymmetric scattering of polarized electrons by organized organic films of chiral molecules. Science, 283, 814–816 (1999).

    CAS  PubMed  Google Scholar 

  15. Carmeli, I., Skakalova, V., Naaman, R. & Vager, Z. Magnetization of chiral monolayers of polypeptide: A possible source of magnetism in some biological membranes. Angew. Chem. Int. Ed. 41, 761–764 (2002).

    CAS  Google Scholar 

  16. Ray, S. G. et al. Chirality-induced spin-selective properties of self-assembled monolayers of DNA on gold. Phys. Rev. Lett. 96, 36–39 (2006).

    Google Scholar 

  17. Mukhopadhyay, P., Zuber, G., Wipf, P. & Beratan, D. N. Contribution of a solutés chiral solvent imprint to optical rotation. Angew. Chem. Int. Ed. 46, 6450–6452 (2007).

    CAS  Google Scholar 

  18. Yin, M. Y. et al. Asymmetric hydrogenation of ketones catalyzed by a silica-supported chitosan–palladium complex. J. Mol. Catal. A Chem. 147, 93–98 (1999).

    CAS  Google Scholar 

  19. Huck, W. R., Mallat, T. & Baiker, A. Heterogeneous enantioselective hydrogenation of 2-pyrones over cinchona-modified palladium. New J. Chem. 26, 6–8 (2002).

    CAS  Google Scholar 

  20. Huck, W. R., Mallat, T. & Baiker, A. Enantioselective hydrogenation of a methoxypyrone with cinchona-modified palladium. Catal. Lett. 80, 87–92 (2002).

    CAS  Google Scholar 

  21. Mhadgut, S. C., Török, M., Esquibel, J. & Török, B. Highly asymmetric heterogeneous catalytic hydrogenation of isophorone on proline modified base-supported palladium catalysts. J. Catal. 238, 441–448 (2006).

    CAS  Google Scholar 

  22. Tungler, A., Fodor, K., Máthé, T. & Sheldon, R. A. Enantioselective hydrogenation of ethyl pyruvate and isophorone over modified Pt and Pd catalysts. In Heterogeneous Catalysis and Fine Chemicals IV. Proc. 4th Int. Symp. on Heterogeneous Catalysis and Fine Chemicals, Basel, 8–12 September 1996. Studies in Surface Science and Catalysis Vol. 108 (eds Blaser, H.-U., Baiker, A., & Prins, R.) 157–165 (Elsevier, 1997).

    Google Scholar 

Download references

Acknowledgements

G.R. and L.D.P. thank the Netherlands Organization for Scientific Research (NWO) for support via the Vernieuwingsimpuls programme. T.Z.M. and R.N. acknowledge the support of the Israel Science Foundation.

Author information

Authors and Affiliations

  1. Van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Nieuwe Achtergracht 166, Amsterdam, 1018, WV, The Netherlands

    L. Durán Pachón & G. Rothenberg

  2. Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem, 91904, Israel

    I. Yosef & D. Avnir

  3. Department of Chemical Physics, Weizmann Institute of Science, Rehovot, 76100, Israel

    T. Z. Markus & R. Naaman

Authors
  1. L. Durán Pachón
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. I. Yosef
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. T. Z. Markus
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. R. Naaman
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. D. Avnir
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. G. Rothenberg
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to G. Rothenberg.

Supplementary information

Supplementary information

Supplementary information (PDF 458 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Durán Pachón, L., Yosef, I., Markus, T. et al. Chiral imprinting of palladium with cinchona alkaloids. Nature Chem 1, 160–164 (2009). https://doi.org/10.1038/nchem.180

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nchem.180

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing